Azo dye with a 2,6-diamino-5-cyano-or-5-carbamoyl-pyridine coupling component

ABSTRACT

A dye of the formula ##STR1## wherein D is the radical of a diazo component, especially phenyl, phenylazophenyl, benzthiazolyl, benzisothiazolyl, thienyl, thiazolyl, thiadiazolyl and substituted derivatives thereof, 
     R is hydrogen or alkyl of 1 to 7 carbon atoms, 
     X is cyano or carbamoyl, 
     A is a hydrocarbon radical, the two 
     A&#39;s together with the nitrogen form a saturated heterocyclic ring, and 
     A 1  is hydrogen or a hydrocarbon radical. 
     The dyes are eminently suitable for coloring synthetic fibers, particularly polyesters, brilliant shades.

This application is a continuation-in-part of our copending applicationSer. No. 209,431, filed Dec. 17, 1971, now abandoned.

The invention relates to dyes of the formula I ##STR2## in which D isthe radical of a diazo component,

R is hydrogen or alkyl of 1 to 7 carbon atoms,

X is cyano or carbamoyl,

A is a hydrocarbon radical, the two

A's together with the nitrogen form a saturated heterocyclic ring, and

A¹ is hydrogen or a hydrocarbon radical.

The radical D may be derived for example from an amine of the benzene,benzothiazole, benzoisothiazole, thiazole, thiadiazole, thiophene,azobenzene or anthraquinone series.

The radical D of the diazo component may for example bear the followingsubstituents:

IN THE BENZENE SERIES: CHLORO, BROMO. NITRO, CYANO, TRIFLUOROMETHYL,METHYLSULFONYL, ETHYLSULFONYL, PHENYLSULFONYL, CARBOMETHOXY,CARBOETHOXY, CARBOBUTOXY, CARBO-β-METHOXYETHOXY, CARBO-β-HYDROXYETHOXY,UNSUBSTITUTED, N-monosubstituted or N,N-disubstituted carbamoyl orsulfamoyl, methyl, ethyl, methoxy or ethoxy; at least one substituent ofthe second order (electron-attracting) should be present. Second ordersubstituents are the above substituents other than chloro, bromo,methyl, ethyl, methoxy and ethoxy.

Examples of N-substituents for the carbamoyl and sulfamoyl groups are:methyl, ethyl, propyl, butyl, β-hydroxyethyl, γ-hydroxypropyl,β-methoxyethyl, γ-methoxypropyl, γ-ethoxypropyl, piperidide, pyrrolidideand morpholide.

In the azobenzene series: chloro, bromo, nitro, cyano, ethyl, methyl,ethoxy, methoxy or ethoxy.

In the heterocyclic series; chloro, bromo, nitro, cyano, methyl, ethyl,phenyl, methoxy, ethoxy, methylmercapto, β-carbomethoxyethylmercapto,β-carboethoxyethylmercapto, carbomethoxy, carboethoxy, acetyl,methylsulfonyl or ethylsulfonyl.

The radical D may be specifically derived for example from the followingamines:

ANILINE, O-TOLUIDINE, M-TOLUIDINE, P-TOLUIDINE, O-NITROANILINE,M-NITROANILINE, P-NITROANILINE, O-CYANOANILINE, M-CYANOANILINE,P-CYANOANILINE, 2,4-DICYANOANILINE, O-CHLOROANILINE, M-CHLOROANILINE,P-CHLOROANILINE, O-BROMOANILINE, M-BROMOANILINE, P-BROMOANILINE,2,4,6-TRIBROMOANILINE, 2-CHLORO-4-NITROANILINE, 2-BROMO-4-NITROANILINE,2-CYANO-4-NITROANILINE, 2-METHYLSULFONYL-4-NITROANILINE,2-METHYL-4-NITROANILINE, 2-METHOXY-4-NITROANILINE,4-CHLORO-2-NITROANILINE, 4-METHYL-2-NITROANILINE,4-METHOXY-2-NITROANILINE, 1-AMINO-2-TRIFLUOROMETHYL-4-CHLOROBENZENE,2-CHLORO-5-AMINOBENZONITRILE, 2-AMINO-5-CHLOROBENZONITRILE,1-AMINO-2-NITROBENZENE-4-SULFONIC ACID N-BUTYLAMIDE ORβ-METHOXYETHYLAMINE, 2,4-DINITROANILINE, 2,4-DINITRO-6-CHLOROANILINE,2,4-DINITRO-6-BROMOANILINE, 2,4-DINITRO-6-CYANOANILINE,1-AMINO-2,4-DINITROBENZENE-6-METHYLSULFONE, 2,6-DICHLORO-4-NITROANILINE,2,6-DIBROMO-4-NITROANILINE, 2-CHLORO-6-BROMO-4-NITROANILINE,2,6-DICYANO-4-NITROANILINE, 2-CYANO-4-NITRO-6-CHLOROANILINE,2-CYANO-4-NITROBROMOANILINE, 1-AMINOBENZENE-4-METHYLSULFONE,1-AMINO-2,6-DIBROMOBENZENE-4-METHYLSULFONE,1-AMINO-2,6-DICHLOROBENZENE-4-METHYLSULFONE,1-AMINO-2,4-DINITROBENZENE-6-CARBOXYLIC ACID METHYL OR β-METHOXYETHYLESTER, 3,5-DICHLOROANTHRANILIC ACID PROPYL ESTER, 3,5-DIBROMOANTHRANILICACID β-METHOXYETHYL ESTER, N-acetyl-p-phenylenediamine,4-aminoacetophenone, 4-aminobenzophenone, 2-aminobenzophenone,2-aminodiphenylsulfone, 4-aminodiphenylsulfone, the methyl, ethyl,propyl, butyl, isobutyl, β-methoxyethyl, β-ethoxyethyl, methyl diglycol,ethyl diglycol, methyl triglycol, ethyl triglycol, β-hydroxyethyl,β-acetoxyethyl, β-(β'-hydroxyethoxy)-ethyl, βhydroxypropyl,γ-hydroxypropyl, ω-hydroxybutyl or ω-hydroxyhexyl ester of2-aminobenzoic acid, 3-aminobenzoic acid or 4-aminobenzoic acid, themethyl, isobutyl, methyl diglycol, β-methoxyethyl, β-butoxyethyl orβ-acetoxyethyl ester of 5-nitroanthranilic acid, the dimethyl, diethyl,dipropyl or dibutyl ester of 3-aminophthalic acid, 4-aminophthalic acid,5-aminoisophthalic acid or aminoterephthalic acid, the amide,methylamide, propylamide, butylamide, isobutylamide, cyclohexylamide,β-ethylhexylamide, γ-methoxypropylamide, or γ-ethoxypropylamide of3-aminobenzoic acid or 4-aminobenzoic acid, the dimethylamide,diethylamide, pyrrolidide, morpholide or N-methyl-N-β-hydroxyethylamideof 2-aminobenzoic acid, 3-aminobenzoic acid or 4-aminobenzoic acid, thediamide or bis-γ-methoxypropylamide of 5-aminoisophthalic acid, thebis-diethylamide of aminoterephthalic acid, the imide,γ-hydroxyethylamide or γ-hydroxypropylamide of 3-aminophthalic acid or4-aminophthalic acid, the β-hydroxyethylamide of 3-amino-6-nitrophthalicacid, the dimethylamide, diethylamide, pyrrolidide or morpholide of2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid or4-aminobenzenesulfonic acid, the 2'-aminophenyl, 3'-aminophenyl or4'-aminophenyl ester of methylsulfonic acid, ethylsulfonic acid,butylsulfonic acid or benzenesulfonic acid, 2-aminoanthraquinone,1-amino-4-chloroanthraquinone, 3-aminodiphenylene oxide,4-aminodiphenylene oxide, 2-aminobenzothiazole, 2-amino-6-carboxylicacid methyl ester benzothiazole, 2-amino-6-methylsulfonylbenzothiazole,2-amino-6-cyanobenzothiazole, 2-amino-6-nitrobenzothiazole,5,6-dichloro-2-aminobenzothiazole, 6,7-dichloro-2-aminobenzothiazole,4-amino-5-bromo-7-nitro-1,2-benzoisothiazole,3-amino-5-nitro-2,1-benzoisothiazole,3-amino-5-nitro-7-bromo-2,1-benzoisothiazole, 2-aminothiazole,2-amino-5-nitrothiazole, 2-amino-4-methylthiazole-5-carboxylic acidethyl ester, 2-amino-4-methyl-5-acetylthiazole,2-amino-3-cyano-4-methylthiophene-5-carboxylic acid esters,2-phenyl-5-amino-1,3,4-thiadiazole, 3-methylmercapto-5-amino-1,2,4-thiadiazole,3-β-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole, or 2,4-dicyano-3,5-dimethylaniline.

Examples of suitable diazo components of the aminoazobenzene series are:4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene,3',2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene,2-methyl-5-methoxy-4-aminoazobenzene,2-methyl-4',5-dimethoxy-4-aminoazobenzene,4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene,4'-nitro-2-methyl-5-methoxy-4-aminoazobenzene,4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminozobenzene,4'-chloro-2,5-dimethoxy-4-aminoazobenzene,4'-nitro-2,5-dimethoxy-4-aminoazobenzene,4'-chloro-2,5-dimethyl-4-aminoazobenzene,4'-methoxy-2,5-dimethyl-4-aminoazobenzene, 4'-nitro-4-aminoazobenzene,3,5dibromo-4-aminoazobenzene, 2,3'-dichloro-4-aminoazobenzene,3-methoxy-4-aminoazobenzene or 4'-hydroxy-2'-methyl-4-aminoazobenzene.

Examples of radicals R (in addition to hydrogen) are: ethyl, n-propyl,isopropyl, butyl, pentyl, ethylpentyl and preferably methyl.

Radicals A¹, apart from hydrogen, are alkyl of one to eight carbonatoms, alkyl substituted by cyano, hydroxy, alkoxy of one to eightcarbon atoms, phenoxy, phenoxyethoxy or benzyloxy, cyclohexyl,norbornyl, benzyl, phenylethyl, phenylhydroxyethyl, phenylpropyl,phenylbutyl, phenyl which may be substituted by methoxy,polyalkoxyalkyl, hydroxypolyalkoxyalkyl, alkanoyloxyalkyl oralkoxycarbonylalkyl.

Examples of cyanoalkyl radicals A¹ are:

(CH₂)₂ --CN, (CH₂)₅ --CN, (CH₂)₆ --CN, (CH₂)₇ --CN, (CH₂)₂ --O--(CH₂)₂--CN, (CH₂)₃ --O--(CH₂)₂ --CN or (CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --CN.

Examples of specific radicals A¹ in addition to those already specifiedare:

1. unsubstituted or substituted akyl: CH₃, C₂ H₅, n--C₃ H₇, i--C₃ H₇,n--C₄ H₉, i--C₄ H₉, C₆ H₁₃, ##STR3## CH₂ CH₂ OH, (CH₂)₃ OH, ##STR4## CH₃--CH--CH₂ OH, (CH₂)₄ OH, (CH₂)₆ OH, ##STR5## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃O(CH₂)₄ OH, (CH₂)₃ OC₂ H₄ OH, (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅,(CH₂)₃ O(CH₂)₆ OH, (CH₂)₃ OC₂ H₄ OCH(CH₃)₂, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃OC₂ H₄ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₂ H₄ C₆ H₅, ##STR6## (CH₂)₃ OC₂ H₄OC₆ H₅, ##STR7## the equivalent radicals in which the groupings --OC₂ H₄--, ##STR8## are present twice; CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂OC₃ H₇, CH₂ CH₂ OC₄ H₉, CH₂ CH₂ OC₆ H₅, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅,(CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR9## (CH₂)₃ OC₆ H₁₃, (CH₂)₃ OC₈ H₁₇,(CH₂)₃ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ C₆ H₅, (CH₂)₃ OC₆ H₅, ##STR10##

2. unsubstituted or substituted cycloalkyl and polycycloalkyl ##STR11##

3. aralkyl: CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR12##

4. phenyl

5. CH₂ CH=CH₂, (CH₂)₂ COOH, (CH₂)₅ COOH and ##STR13## in which n is 2,3, 4 or 6, C₂ H₄ OCOCH₃, C₂ H₄ OCHO, C₂ H₄ OCOCH₃, (C₂ H₄ O)₂ COCH₃, (C₂H₄ O)₂ CHO, (CH₂)₃ OCOCH₃, (CH₂)₃ OCHO and C₂ H₄ OCOC₂ H₄ COOH.

Examples of preferred substituents A¹ are hydrogen, CH₃, C₂ H₅, n-C₃ H₇,i-C₃ H₇, n-C₄ H₉, i-C₄ H₉, C₆ H₁₃, CH₂ CH₂ OH, (CH₂)₃ OH, ##STR14##(CH₂)₄ OH, (CH₂)₆ OH, ##STR15## (CH₂)₂ -O-(CH₂)₂ OH, (CH₂)₃ O(CH₂)₂ OH,(CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₆ OH, ##STR16## CH₂ CH₂ OCH₃, CH₂ CH₂OC₂ H₅, CH₂ CH₂ OC₄ H₉, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇,(CH₂)₃ OC₄ H₉, ##STR17## (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₄ H₉,(CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR18## or C₆ H₅

Radicals A are for example: alkyl of 1 to 4 carbon atoms, hydroxyalkylof 2 or 3 carbon atoms, alkoxyalkyl of 1 to 4 carbon atoms in the alkoxyand 2 or 3 in the alkyl, cyclohexyl or phenyl.

Specific radicals ##STR19## are e.g.: N(CH₃)₂, N(C₂ H₅)₂, N(C₃ H₇)₂,N(C₄ H₉)₂, ##STR20## N(C₂ H₄ OH)₂, N(CH₂ CH₂ CH₂ OH)₂, N(CH₂ CHOHCH₃)₂,N(C₂ H₄ OCH₃)₂, N(C₂ H₄ OC₂ H₅)₂, N(C₂ H₄ OC₄ H₉)₂, ##STR21##

Preferred radicals ##STR22## are: N(CH₃)₂, N(C₂ H₅)₂, N(C₃ H₇)₂, N(C₄H₉)₂, N(C₂ H₄ OH)₂, ##STR23##

The production of the coupling components is carried out by reacting acompound of the formula ##STR24## wherein Hal is chloro or bromo, firstwith the amine of the formula A¹ -NH₂ and then with the secondary amine##STR25##

When following this sequence, the main product is the isomer of theformula ##STR26## which is contaminated with the isomer of the formula##STR27## Only the isomer IIIa gives valuable dyes. The productsobtained by coupling a diazonium salt with the compounds of the formulaIIIb are obviously unstable and decompose under dyeing conditionswithout influencing the quality of the dyeing. It is therefore notnecessary to separate the isomers IIIa and IIIb.

Dyes of the formula (I) are prepared by reacting a diazo compound of anamine of the formula (II):

    d--nh.sub.2                                                ii

with a coupling component of the formula (IIIa): ##STR28## in which D,R, X, A and A¹ have the above meanings.

The amines are diazotized by conventional methods. Coupling is similarlycarried out conventionally in aqueous medium with or without adding asolvent, at a strongly to weakly acid reaction.

Specific features of the production of the coupling components and dyesmay be taken from the Examples.

In particular, the invention relates to dyes of the formula ##STR29##wherein D¹ is phenyl substituted by chlorine, bromine, trifluoromethyl,methyl, ethyl, methoxy, nitro, cyano, methylsulfonyl, ethylsulfonyl,phenylsulfonyl, carbalkoxy of a total of 2 to 5 carbon atoms,carbo-β-alkoxyethoxy, said alkoxy having 1 to 4 carbon atoms, orN,N-dialkylsubstituted sulfamoyl, said alkyl having 1 to 3 carbon atoms;phenylazophenyl; phenylazophenyl substituted by methyl, chlorine,bromine or nitro; benzthiazolyl; benzthiazolyl substituted by nitro,cyano, methylsulfonyl or ethylsulfonyl; benziothiazolyl substituted bychlorine, bromine, cyano or nitro; thiazolyl substituted by cyano ornitro; thienyl substituted by methyl, cyano, nitro or carbalkoxy of atotal of 2 to 5 carbon atoms; or thiadiazolyl substituted by phenyl,methyl, chlorine, bromine, methylmercapto, ethylmercapto oralkoxycarbonylethylmercapto; said alkoxy having 1 to 4 carbon atoms;

R¹ is hydrogen or alkyl of 1 to 3 carbon atoms;

X is carbamoyl or cyano;

A³ is hydrogen, alkyl of 1 to 8 carbon atoms; alkyl of 2 to 8 carbonatoms substituted by hydroxy, OCHO, OCOCH₃, hydroxyalkoxy of 2 to 4carbon atoms, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy or phenyl;cyclohexyl; norbornyl; phenyl; β-hydroxy-β-phenylethyl; or CH₂)₃ (OC₂H₄)_(m) OT and T is alkyl of 1 to 4 carbon atoms, benzyl or phenyl, m is1 or 2;

A² is alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 2 or 3 carbon atoms,alkoxyalkyl of 1 to 4 carbon atoms in the alkoxy and 2 or 3 carbon atomsin the alkyl, cyclohexyl or phenyl and ##STR30## is pyrrolidino,piperidino, morpholino, hexamethyleneimino, piperazino,N-methylpiperazino or N-β-hydroxyethylpiperazino.

Dyes and dye mixtures of the formula (Ia) are particularly valuableindustrially: ##STR31## in which B is nitro, cyano, chloro, bromo,carbomethoxy, carboethoxy, β-methoxycarboethoxy, methylsulfonyl,ethylsulfonyl, methyl, methoxy or phenylazo;

B¹ is hydrogen, nitro, chloro, bromo, cyano, methyl, methoxy,carbomethoxy, caroethoxy, methylsulfonyl or ethylsulfonyl; and

B² is hydrogen, chloro, bromo, cyano, methyl, methoxy, carbomethoxy orcarboethoxy;

A⁴ is hydrogen, alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 to 8carbon atoms, alkoxyalkyl of 2 or 3 carbon atoms in the alkyl and 1 to 8carbon atoms in the alkoxy, CH₂ CH₂ OC₂ CH₂ OH, (CH₂)₃ OCH₂ CH₂ OH,(CH₂)₃ O(CH₂)₄ OH or (CH₂)₃ (OC₂ H₄)_(p) OT,

p is 0, 1 or 2,

T is alkyl of 1 to 4 carbon atoms, benzyl or phenyl, and ##STR32## isN(CH₃)₂, N(C₂ H₅).sub. 2, N(C₃ H₇)₂, N(C₄ H₉)₂, N(C₂ H₄ OH)₂, ##STR33##

The corresponding dyes which contain as diazo components: benzothiazole,benzoisothiazole, thiazole, thiadiazole or thiophene which may besubstituted by nitro, chloro, bromo, cyano, methyl, methylmercapto,β-carbomethoxyethylmercapto, β-carboethoxyethylmercapto, carbomethoxy,carboethoxy or acetyl are also particularly valuable.

The following specific diazo components are particularly valuable:4-nitroaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline,2-cyano-4-nitroaniline, 2-methoxy-4-nitroaniline,2-amino-5-nitrophenylsulfonic acid dimethylamide,2-amino-5-nitrophenylsulfonic acid butylamide,2-amino-5-nitrophenylsulfonic acid β-methoxyethylamide,2-aminobenzonitrile, 3-chloro-4-aminobenzonitrile,2-chloro-5-aminobenzonitrile, 2-amino-5-chloro-benzonitrile,3,5-dichloro-2-aminobenzonitrile, 1-amino-2,4-dicyanobenzene,1-amino-2,4-dicyano-6-chlorobenzene,2-chloro-4-amino-5-nitrbenzonitrile, 2-amino-3-bromo-5-nitrobenzonitrile, 2,6-dicyano-4-nitroaniline,2,5-dichloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline,2,6-dibromo-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline,2,4-dinitroaniline, 2,4-dinitro-6-chloroaniline,2,4-dinitro-6-bromoaniline, 2-amino-3,5-dinitrobenzonitrile,1-amino-4-nitrobenzene-2-methylsulfone,1-amino-4-nitrobenzene-2-ethylsulfone, 4-methylsulfonyl-aniline,1-amino-2-chlorobenzene-4-methylsulfone,1-amino-2,6-dibromobenzene-4-methylsulfone,1-amino-2,6-dichlorobenzene-4-methylsulfone, esters of 2-aminobenzoicacid, 4-aminobenzoic acid, 2-amino-5-nitrobenzoic acid,2-amino-3-chloro-5-nitrobenzoic acid, 2-amino-3,5-dichlorobenzoic acidand 2-amino-3,5-dibromobenzoic acid, the methyl or β-methoxyethyl esterof 2-amino-3,5-dinitrobenzoic acid, diethyl 2-aminoterephthalate,4-aminoazobenzene, 2,3'-dimethyl-4-aminoazobenzene,2',3-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene,3,5-dibromo-4-aminoazobenzene and 2,4-dicyano-3,5-dimethylaniline.

Examples of particularly valuable heterocyclic diazo components are asfollows: 2-amino-5-nitrothiazole, 2-amino-4-methyl-5-nitrothiazole,2-amino-4-methylthiazole 5-carboxylic acid ethyl ester,2-amino-5-phenyl-1,3,4-thiadiazole, 3-phenyl-5-amino-1,2,4-thiadiazole,3-methylmercapto-5-amino-1,2,4-thiadiazole, 3-62-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole,3-β-carboethoxyethylmercapto-5-amino-1,2,4-thiazole,2-amino-6-cyanobenzothiazole, 2-amino-6-caboxylic acid methyl esterbenzothiazole, 2-amino-6-nitrobenzothiazole,2-amino-3-cyano-4-methylthiophene-5-carboxylic esters,3-amino-5-nitro-2,1-benzoisothiazole,3-amino-5-nitro-7-chloro-2,1-benzoisothiazole,3-amino-5-nitro-7-bromo-2,1-benzoisothiazole,4-amino-7-nitro-1,2-benzoisothiazole,4-amino-5-bromo-1,2-benzoisothiazole,4-amino-5-bromo-7-nitro-1,2-benzoisthiazole,4-amino-5-cyano-7-nitro-1,2-benzoisothiazole and4-amino-5-chloro-7-nitro-1,2-benzoisothiazole.

The new dyes are yellow to blue and are suitable for dyeing textilematerials of acrylonitrile polymers, synthetic polyamides, celluloseesters such as secondary cellulose acetate or triacetate, andparticularly of synthetic linear polyesters such as polyethylene glycolterephthalate, or polymers having an analogous chemical constitution.

The dyes are also suitable for dyeing in organic solvents such asperchloroethylene and also for the process known as transfer printingprovided they sublime at a temperature of from 160° to 240° C. Inparticular they may be applied however from aqueous dispersion and bythe thermosol method. Deep shades are obtained which have excellentfastness properties, particularly fastness to light and heat setting.

The following Examples illustrate the invention. References to parts andpercentages are by weight unless otherwise stated.

EXAMPLE 1

187 parts of 2,6-dichloro-3-cyano-4-methylpyridine is stirred at 40° Cfor 5 hours with 420 parts of a 21% aqueous methylamine solution. Themixture is then diluted with water, filtered, and the residue washedwith water and dried, 182 parts of a colorless product (m.p. 136° to141° C) is obtained which is recrystallized from 3000 parts by volume ofbenzene. There is obtained about 84 parts of the product of the formulaI ##STR34## The product is sparingly soluble in benzene. The residueobtained after removal of the benzene and recrystallization is approx.84 parts of the product of the formula II ##STR35## 181.5 parts of theproduct of formula I is stirred with 600 parts by volume of 50% aqueousdimethylamine solution for 6 hours in an autoclave at 140° to 150° C.The mixture is allowed to cool, acidified with concentrated hydrochloricacid and filtered. The filtrate is neutralized to pH 4 to 5, and theprecipitate is isolated as usual and dried. 140 parts of the couplingcomponent of the formula III ##STR36## is obtained. It is colorless,melts at 119° and dissolves readily in chloroform.

By treating 2-methylamino-3-cyano-4-methyl-6-chloropyridine (II) withdimethylamine in the same manner, coupling component IV ##STR37## isobtained, which however affords less satisfactory dyes.

7.6 parts of the product of formula III is dissolved in 50 parts byvolume of dimethylformamide and the solution combined with a diazosolution, cooled to 0° C, of 7.8 parts oftrifluoromethyl-4-chloroaniline, which has been diazotized in sulfuricacid as usual. The pH of the coupling mixture is raised to 2.5 to 3 withsodium acetate at 0° to 5° C.

Upon completion of the coupling, the dye of the formula ##STR38## isfiltered off, washed with water and dried. Approx. 15 parts of a yellowpowder is obtained which colors polyethylene terephthalate fabric yellowshades having good lightfastness. As the dye readily sublimes it issuitable for transfer printing methods.

EXAMPLE 2

187 parts of 2,6-dichloro-3-cyano-4-methylpyridine is stirred at 40' to45° C for 6 hours with a mixture of 250 parts of 2-hydroxyethylamine and250 parts by volume of water. Then 2,000 parts by volume of cold wateris added and the precipitate filtered off, washed with water and dried.202 parts of a colorless powder melting at 130° C is obtained. Thepowder consists of a mixture of the products of the formulae ##STR39##106 parts of this mixture is stirred in an autoclave for 5 hours at 140°to 150° C with 250 parts of diethylamine. After cooling and isolation,110 parts of a colorless powder melting at 73° C is obtained. The powderis a mixture of the products of the formulae ##STR40## 9.9 parts of thismixture is dissolved in 30 parts of dimethylformamide and the mixtureadded to a diazonium salt solution at 0° C obtained as follows:

9.7 parts of 2-amino-3-bromo-5-nitrobenzontrile is added at 0° to 5° Cto a mixture of 40 parts of 96% sulfuric acid and 13 parts of 44%nitrosylsulfuric acid. The mixture is stirred for 5 hours at 0° to 5° Cand then poured onto ice with continued stirring. Then someamidosulfonic acid is added followed by the coupling component(s).Coupling is rapidly completed by raising the pH to 2.5 with 25% causticsoda solution at 0° to 5° C. After filtration, washing and drying, 19.0parts of a dark red powder is obtained which dissolves indimethylformamide with a violet color and colors polyethyleneterephthalate fabric deep shades having good fastness to light anddry-heat pleating and setting. The coloration is produced by the dye ofthe formula ##STR41## whereas the dye of the formula ##STR42## which isalso contained in the powder is destroyed in the dyeing process.

EXAMPLE 3

106 parts of the mixture of the compounds of the formulas ##STR43##described in Example 2 is stirred with 360 parts by volume ofpyrrolidine in an autoclave for 6 hours at 140° to 150° C. Aftercooling, the resultant colorless product is filtered off, washed withwater and dried. 120 parts of a mixture of the compounds of the formulas##STR44## melting at 118° C is obtained.

9.9 parts of this mixture is dissolved in 30 parts by volume ofdimethylformamide and the solution added to 9.7 parts of2-amino-3-bromo-5-nitrobenzonitrile which has been diazotized and pouredonto ice in accordance with Example 2. The pH of the mixture is raisedto 2.5 with 50% caustic soda solution and the precipitated dye filteredoff, washed with water and dried. 19 parts of a reddish brown powder isobtained which dissolved in dimethylformamide with a violet color andcolors polyethylene terephthalate material ruby shades having goodfastness to light and dry-heat pleating and setting.

The coloration is produced by the dye of the formula ##STR45## whereasthe dye of the formula ##STR46## which is also contained in the powderis destroyed in the dyeing process.

The dyes identified in the following Tables are obtained analogously.

                                      TABLE 1                                     __________________________________________________________________________     ##STR47##                                                                    __________________________________________________________________________    No.                                                                              D              R.sup.1   R.sup.2                                                                              R.sup.3                                                                              Shade                               __________________________________________________________________________     4                                                                               C.sub.2 H.sub.4 OH                                                                           C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      yellow                                      5                                                                               "##STR49##     "         "      "                                           6                                                                               CH.sub.2 CH.sub.2 OCH.sub.3                                                                  CH.sub.3  CH.sub.2 CH.sub.2 OH                                                                 red                                         7 "              CH.sub.2 CH.sub.2 OH                                                                    C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      red                                  8                                                                               CH.sub. 2 CH.sub.2 OCH.sub.3                                                                 CH.sub.3  CH.sub.2 CH.sub.2 OH                                                                 ruby                                        9                                                                               "##STR52##     C.sub.2 H.sub.5                                                                         "      blue                                       10                                                                               CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                      "         C.sub.2 H.sub.5                                                                      red                                        11 "              "         C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.7 (n)                                                                  "                                   12 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   13 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      "                                   14                                                                               CH.sub.2 CH.sub.2 OH                                                                         "         "      yellowish red                              15 "              "         CH.sub.3                                                                             CH.sub.3                                                                             "                                   16 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      "                                   17 "              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub. 2 OH                                                "      "      "                                   18 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           CH.sub.3                                                                             CH.sub.3                                                                             "                                   19                                                                               "##STR55##     "         "      orange                                     20 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   21 "              "         C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      "                                   22 "              CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                       CH.sub.2 CH.sub.2 OH                                                                 CH.sub.2 CH.sub.2 OH                                                                 "                                   23 "              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      "                                   24                                                                               CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3  CH.sub.3                                                                             yellowish red                              25 "              "         C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      "                                   26 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   27 "                                                                                            "##STR57##                                                                              "      "                                          28                                                                               "##STR58##     C.sub.2 H.sub.4 OCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            yellow                                     29 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   30                                                                               "##STR59##     "         "      "                                          31 "              CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                        CH.sub.2 CH.sub.2 OH                                                                 CH.sub.3                                                                             "                                   32 "              "         "      CH.sub.2 CH.sub.2 OH                                                                 "                                   33 "                                                                                            "##STR60##                                                                              "      yellow (polyamide)                         34 "                                                                                            "##STR61##                                                                              CH.sub.3                                                                             "                                          35                                                                               "##STR62##     "         "      "                                          36 "              CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                             CH.sub.2 CH.sub.2 OH                                                                 CH.sub.2 CH.sub.2 OH                                                                 "                                   37 "              (CH.sub.2).sub.6 OH                                                                     CH.sub.2 CH.sub.2 OCH.sub.3                                                          CH.sub.2 CH.sub.2 OCH.sub.3                                                          "                                   38                                                                               CH.sub.2 CH.sub.2 OH                                                                         C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      red                                        39 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   40 "              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                 "      "      "                                   41                                                                               "##STR64##     "         "      "                                          42 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   43                                                                               "##STR65##     "         "      bluish red                                 44 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   45 "              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                 "      "      "                                   46                                                                               "##STR66##     "         "      ruby                                       47 "              "         CH.sub.3                                                                             CH.sub.3                                                                             "                                   48                                                                               CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                      C.sub.3 H.sub.7 (n)                                                                     C.sub.3 H.sub.7 (n)                                                                  "                                          49                                                                               "##STR68##     "         "      bluish red                                 50 "              "         C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      "                                   51                                                                               "##STR69##     "         "      orange                                     52 "              CH.sub.2 CH.sub.2 OH                                                                    CH.sub.3                                                                             CH.sub.2 CH.sub.2 OH                                                                 "                                   53 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   54                                                                               "##STR70##     "         "      "                                          55                                                                               "##STR71##     C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      bluish red                                 56 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   57 "              "         CH.sub.3                                                                             CH.sub.3                                                                             "                                   58 "              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      "                                   59                                                                               "##STR72##     "         "      violet                                     60                                                                               "##STR73##     "         "      navy                                       61 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   62 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   63 "               "        "      "      "                                   64 "              "         CH.sub.3                                                                             CH.sub.3                                                                             "                                   65 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   66                                                                               "##STR74##     C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      blue                                       67 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   68                                                                               "##STR75##     "         "      orange                                     69 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   70                                                                               CH.sub.2 CH.sub.2 OH                                                                         C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      "                                          71 "              "         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub. 2 H.sub.4 OCH.sub.3                                                           "                                   72                                                                               CH.sub.2 CH.sub.2 OH                                                                         C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      yellowish                                                                            red                                 73 "              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                 "      "      "                                   74                                                                               "##STR78##     "         "      bluish red                                 75 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   76                                                                               "##STR79##     "         "      red                                        77 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   78 "              CH.sub.2 CH.sub.2 OH                                                                    C.sub.4 H.sub.9 (n)                                                                  C.sub.4 H.sub.9 (n)                                                                  "                                   79                                                                               "##STR80##     C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      yellow                                     80 "              "         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            yellow                                                                        (poly-                                                                        amide)                              81 "              "         C.sub.2 H.sub.4 OH                                                                   C.sub.2 H.sub.4 OH                                                                   "                                   82                                                                               "##STR81##     C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      yellowish red                              83                                                                               "##STR82##     "         "      "                                          84 "              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                 "      "      "                                   85                                                                               "##STR83##     "         "      "                                          86 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   87                                                                               "##STR84##     "         "      red                                        88 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   89 "              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                 "      "      "                                   90                                                                               "##STR85##     "         "      yellow                                     91 "                                                                                            CH.sub.3##                                                                              CH.sub.2 CH.sub.2 OH                                                                 yellow (polyamide)                         92 "                                                                                            CH.sub.2 CH.sub.2 OH                                                                    CH.sub.2 CH.sub.2 OH                                                                 "                                          93                                                                               CH.sub.2 CH.sub.2 OH                                                                         C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      bluish red                                 94 "              CH.sub.2 CH.sub.2 CH.sub.2 OH                                                           "      "      "                                   95                                                                               "##STR89##     "         "      yellow (polyamide)                         96                                                                               "##STR90##     "         "      violet                                     97 "              CH.sub.2 CH.sub.2 OH                                                                    "      "      "                                   98 "              "         C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.7 (n)                                                                  "                                   99                                                                               "##STR91##     C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                      yellow                                     __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR92##                                                                    __________________________________________________________________________    No.                                                                              D            X            R.sup.1      R.sup.2                                                                             Shade                         __________________________________________________________________________    100                                                                               ##STR93##                                                                    CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                    CH.sub.3     yellow                                           101                                                                              "            "            "            C.sub.3 H.sub.7 (n)                                                                 "                             102                                                                              "                                                                                          "##STR95##   "            "                                   103                                                                              "##STR96##   "            CH.sub.3     orange                              104                                                                              "                                                                                          "##STR97##   "            "                                   105                                                                              "            "            CH.sub.2 CH.sub.2 OH                                                                       "     "                             106                                                                              "##STR98##   "            "            "                                   107                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "H    "                             108                                                                              "            "            "            C.sub.2 H.sub.5                                                                     "                             109                                                                              "            "            "            C.sub.3 H.sub.7 (n)                                                                 "                             110                                                                              "##STR99##   "            C.sub.2 H.sub.5                                                                            red                                 111                                                                              "            "            CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              CH.sub.3                                                                            "                             112                                                                              "##STR100##  "            "            "                                   113                                                                              "            "            CH.sub.2 CH.sub.2 OH                                                                       "     "                             114                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "H                                  115                                                                              "                                                                                          (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                       "            red                                 116                                                                              "##STR102##  "            "            "                                   117                                                                               ##STR103##                                                                   CH.sub.2 CH.sub.2 OH                                                                       "            ruby                                             118                                                                              "            "            CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              "     reddish                                                                       violet                        119                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "H    ruby                          120                                                                              " #STR105##  CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              "            reddish violet                      121                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "H    ruby                          122                                                                              "            "            "            C.sub.2 H.sub.5                                                                     "                             123                                                                              "                                                                                          "##STR106##  CH.sub.3     "                                   124                                                                              "##STR107##  "            "            "                                   125                                                                              "##STR108##  "            "            violet                              126                                                                              "                                                                                          "##STR109##  "            "                                   127                                                                              "            "            CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              "     "                             128                                                                              "##STR110##  "            "            "                                   129                                                                              "##STR111##  "            "            reddish violet                      130                                                                              "            "            CH.sub.2 CH.sub.2 OH                                                                       "     "                             131                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "H    "                             132                                                                              "                                                                                          "##STR112##  "            ruby                                133                                                                              "##STR113##  "            "            red                                 134                                                                              "                                                                                          "##STR114##  "            "                                   135                                                                              "##STR115##  "            "            "                                   136                                                                              "                                                                                          "##STR116##  "            "                                   137                                                                              "##STR117##  "            "            "                                   138                                                                               ##STR118##                                                                   CH.sub.2 CH.sub.2 OH                                                                       "            yellow                                           139                                                                              "            "            CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              "     "                             140                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "H    "                             141                                                                              "                                                                                          "##STR120##  "            "                                   142                                                                              "                                                                                          CH.sub.2 CH.sub.2 OH                                                                       "            "                                   143                                                                              "                                                                                          "##STR122##  "            "                                   144                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "H    "                             145                                                                              "##STR123##  "            "            "                                   146                                                                              "                                                                                          "##STR124##  "            "                                   147                                                                              "            "            CH.sub.2 CH.sub.2 OH                                                                       "     "                             148                                                                              "            "            "            C.sub.3 H.sub.7 (n)                                                                 "                             149                                                                               ##STR125##                                                                   "##STR126##  CH.sub.3     violet                                           150                                                                              "            "            CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              "     "                             151                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "H    "                             152                                                                              "                                                                                          "##STR127##  "            reddish violet                      153                                                                              "##STR128##  "            "            red                                 154                                                                               ##STR129##                                                                   "##STR130##  "            ruby                                             155                                                                              "                                                                                          "##STR131##  "            reddish violet                      156                                                                              "##STR132##  "            "            violet                              157                                                                               ##STR133##                                                                   CH.sub.2 CH.sub.2 OH                                                                       "            yellow (polyamide)                               158                                                                              "                                                                                          "##STR135##  "            yellow                              159                                                                              "                                                                                          "##STR136##  "            "                                   160                                                                               ##STR137##                                                                   CH.sub.2 CH.sub.2 OH                                                                       "            red                                              161                                                                              "            "            CH.sub.2 CH.sub.2 CH.sub.2 OH                                                              "     "                             162                                                                              "##STR139##  "            "            orange                              163                                                                               ##STR140##                                                                   (CH.sub.2).sub.5 CN                                                                        "            yellow                                           164                                                                              "##STR142##  "            "            "                                   165                                                                              "            "            CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                       "CHO  "                             166                                                                               ##STR143##                                                                   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                    "            yellowish red                                    __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR145##                                                                   __________________________________________________________________________    No. D               R.sup.1     A         X    Shade                          __________________________________________________________________________    167                                                                               CH.sub.2 CH.sub.2 OH                                                                          CN#STR147## yellow (polyamide)                            168                                                                               "##STR148##                                                                                   CONH.sub.2# red                                           169 "               "                                                                                         "##STR150##                                                                             "                                   170 "               CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                   "         "    "                              171                                                                               "##STR151##     "           "         "                                   172                                                                               CH.sub.2 CH.sub.2 OH                                                                          "           "         yellow                              173                                                                               CH.sub.2 CH.sub.2 OH                                                                          CN#STR154## ruby                                          174                                                                               CH.sub.2CHCH.sub.2                                                                            "##STR156## yellow                                        175                                                                               CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                          "##STR158## reddish violet                                176 "               CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                   "         CONH.sub.2                                                                         violet                         177                                                                               "##STR159##     "           "         "                                   __________________________________________________________________________

We claim:
 1. A dye of the formula ##STR160## where D¹ is phenylsubstituted by chlorine, bromine, trifluoromethyl, methyl, ethyl,methoxy, nitro, cyano, methylsulfonyl, ethylsulfonyl, phenylsulfonyl,carbalkoxy of a total of 2 to 5 carbon atoms, carbo-β-alkoxyethoxy, saidalkoxy having 1 to 4 carbon atoms or N,N-dialkyl-substituted sulfamoyl,said alkyl having 1 to 3 carbon atoms; phenylazophenyl; phenylazophenylsubstituted by methyl, chlorine, bromine or nitro; benzthiazolyl;benzthiazolyl substituted by nitro, cyano, methylsulfonyl orethylsulfonyl; benzisothiazolyl substituted by chlorine, bromine, cyanoor nitro; thiazolyl substituted by cyano or nitro; thienyl substitutedby methyl, cyano, nitro or carbalkoxy of a total of 2 to 5 carbon atoms;or thiadiazolyl substituted by phenyl, methyl, chlorine, bromine,methylmercapto, ethylmercapto or alkoxycarbonylethylmercapto, saidalkoxy having 1 to 4 carbon atoms;R¹ is hydrogen or alkyl of 1 to 3carbon atoms; X is carbamoyl or cyano; A³ is hydrogen, alkyl of 1 to 8carbon atoms; alkyl of 2 to 8 carbon atoms substituted by hydroxy, OCHO,OCOCH₃, hydroxyalkoxy of 2 to 4 carbon atoms, cyano, alkoxy of 1 to 8carbon atoms, phenoxy or phenyl; cyclohexyl; norbornyl; phenyl;β-hydroxy-β-phenylethyl; or (CH₂)₃ (OC₂ H₄)_(m) OT and T is alkyl of 1to 4 carbon atoms, benzyl or phenyl, m is 1 to 2, each A², which can bethe same or different, is alkyl of 1 to 4 carbon atoms, hydroxyalkyl of2 or 3 carbon atoms, alkoxyalkyl of 1 to 4 carbon atoms in the alkoxyand 2 or 3 carbon atoms in the alkyl, cyclohexyl or phenyl and##STR161## is pyrrolidino, piperidino, morpholino, hexamethyleneimino,piperazino, N-methylpiperazino or N-β-hydroxyethylpiperazino.
 2. A dyeaccording to the formula in claim 1, wherein D¹ is ##STR162## B isnitro, cyano, chloro, bromo, trifluoromethyl, carbomethoxy, carboethoxy,carbo-β-methoxyethoxy, methylsulfonyl, ethylsulfonyl or phenylazo,B¹ ishydrogen, nitro, chloro, bromo, cyano, methyl, methoxy carbomethoxy orcarboethoxy and B² is hydrogen, chloro or cyano.
 3. A dye according tothe formula in claim 1, where X is cyano.
 4. A dye as claimed in claim 1of the formula ##STR163## wherein B is nitro, cyano, chloro, bromo,carbomethoxy, carboethoxy, β-methoxycarboethoxy, methylsulfonyl,ethylsulfonyl, methyl, methoxy or phenylazo;B¹ is hydrogen, nitro,chloro, bromo, cyano, methyl, methoxy, carbomethoxy, carboethoxy,methylsulfonyl or ethylsulfonyl; and B² is hydrogen, chloro, bromo,cyano, methyl, methoxy, carbomethoxy or carboethoxy; A⁴ is hydrogen,alkyl of 1 to 8 carbon atoms, hydroxyalkyl of 2 to 8 carbon atoms,alkoxyalkyl of 2 or 3 carbon atoms in the alkyl and 1 to 8 carbon atomsin the alkoxy, CH₂ CH₂ OCH₂ CH₂ OH, (CH₂)₃ OCH₂ CH₂ OH, (CH₂)₃ O(CH₂)₄OH or (CH₂)₃ (OC₂ H₄)_(p) OT, p is 1 or 2, T is alkyl of 1 to 4 carbonatoms, benzyl or phenyl, and ##STR164## is N(CH₃)₂, N(C₂ H₅)₂, N(C₃H₇)₂, N(C₄ H₉)₂, N(C₂ H₄ OH)₂, ##STR165##
 5. A dye according to theformula in claim 1 where A³ is alkyl of 1 to 6 carbon atoms,hydroxyalkyl of 2 to 6 carbon atoms, alkoxyethyl of a total of 3 to 5carbon atoms, alkoxypropyl of a total of 4 to 6 carbon atoms,phenylalkyl of a total of 7 to 10 carbon atoms, cyclohexyl, norbornyl,β-hydroxy-β-phenylethyl, phenoxyethyl, phenoxypropyl, benzyloxypropyl,γ-phenoxyethoxypropyl, CH₂ CH₂ OCH₂ CH₂ OH, (CH₂)₃ OCH₂ CH₂ OH, (CH₂)₃O(CH₂)₄ OH or (CH₂)₃ (OC₂ H₄)_(m) OT¹, T¹ is alkyl of 1 to 4 carbonatoms and m is 1 or
 2. 6. A dye according to the formula in claim 1where ##STR166## is N-(CH₃)₂, N(C₂ H₅)₂, N(C₃ H₇)₂, N(C₄ H₉)₂, N(C₂ H₄OH)₂, ##STR167##
 7. A dye of the formula ##STR168## in which D¹ has themeanings given in claim 2,A³ has the meanings given in claim 5 and##STR169## has the meanings given in claim
 6. 8. The dye of the formula##STR170##
 9. The dye of the formula ##STR171##
 10. The dye of theformula ##STR172##
 11. The dye of the formula ##STR173##
 12. The dye ofthe formula ##STR174##
 13. The dye of the formula ##STR175##
 14. The dyeof the formula ##STR176##